JPH075491B2 - Dienols and their esters, and processes for their production - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel dienoles and their esters, and a process for producing them. The dienols or esters thereof provided by the present invention are useful as a fragrance component of various fragrance compositions, and are also useful as fragrance components of various fragrance compositions. It is also useful as a synthetic intermediate for an aliphatic monocarboxylic acid ester.

[0002]

BACKGROUND OF THE INVENTION A dieno having a prenyl group at one end and a double bond at the other end and a hydroxyl group at the 4 to 6 carbon atoms from the terminal carbon atom forming the terminal double bond. -, As 8-le, 4,8-dimethyl-1,7-
Nonadiene-4-ol (refer to JP-A-57-11978), 4,5,8-trimethyl-5-vinyl-1,
8-decadiene-4-ol [Chemistry Letters
(Chemistry Letters), No. 5, pp. 527-528 (1979)] and the like.

[0003]

It is desirable to provide a compound having an odor different from that of conventional fragrance materials in order to change the fragrance of the prepared fragrance. Accordingly, one object of the present invention is an aromatic compound having a top note accompanied by mossy and violet leaf-like green notes, and having an animalic and powdery aroma, and It is an object of the present invention to provide a novel dienole or an ester thereof, which has a strong diffusibility and an aroma retaining property, and has excellent properties that are well matched with many perfume materials. Another object of the present invention is to provide a method for producing such a novel dienole or its ester.

[0004]

SUMMARY OF THE INVENTION According to the present invention, one of the objects set forth above is represented by the general formula (I)

[0005]

[Chemical 7]

This is accomplished by providing a diene or an ester thereof represented by

In the above general formula (I), R ↑ 1, R ↑
2, R ↑ 3 and R ↑ 4 are the same or different and each is a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an n-pentyl group, etc. Represents a lower alkyl group.

Y represents a hydrogen atom or a lower acyl group such as a formyl group, an acetyl group, a propionyl group and a butyryl group.

M represents an integer of 1 or 2 and n represents an integer of 0 or 1.

The dienole represented by the general formula (I) or its ester provided by the present invention has a prenyl group at one end and a double bond at the other end, and this terminal double bond is A linear secondary alcohol or a lower aliphatic monocarboxylic acid ester thereof which is characterized by having a hydroxyl group or a lower acyloxy group at the carbon atom at the 4th to 6th positions from the terminal carbon atom to be formed. It is an unlisted novel compound.

These dienols and their esters are
It is a mossy moss leaf top note with green leaf-like notes, and is an aromatic compound with an animalic and powdery odor, and also has strong diffusibility and aroma retention, It is useful as an aroma component of various fragrance compositions because it has excellent properties that are in good harmony with the fragrance materials.

The dienols and their esters are
The aromatic compounds having a typical woody note which is useful as an aroma component of various perfume compositions found by the present inventors and has a typical woody note reminiscent of a vetiver-like aroma and a fernwood-like aroma. , 6-pentamethyl-2,3,3a,
General formula (II) represented by 4,5,7a-hexahydro-1H-inden-2-yl acetate

[0013]

[Chemical 8]

(Where R ↑ 1, R ↑ 2, R ↑ 3, R ↑ 4
, Y, m, and n are as defined above), and are also useful as synthetic intermediates for the bicyclic alcohol or its lower aliphatic monocarboxylic acid ester.

Further, according to the present invention, the above-mentioned other object is achieved by providing the following production method of the diene represented by the general formula (I) or its ester.

That is, the general formula (III)

[Chemical 9]

(Wherein R ↑ 1, R ↑ 2 and m are as defined above, and l represents an integer of 0 or 1) and an oxygen-containing olefin represented by the general formula (IV-1)

[0018]

[Chemical 10]

(Wherein R ↑ 3, R ↑ 4 and n are as defined above and X represents a halogen atom) and / or the general formula (IV-
2)

[0020]

[Chemical 11]

By reacting with an organomagnesium compound represented by the formula (wherein R ↑ 3, R ↑ 4, X and n are as defined above), the compound represented by the general formula (I-1)

[0022]

[Chemical 12]

(Wherein R ↑ 1, R ↑ 2, R ↑ 3, R ↑ 4
, M and n are as defined above).

Then, the diene is reacted with a lower aliphatic monocarboxylic acid or a reactive derivative thereof to give a compound of the general formula (I-2)

[0025]

[Chemical 13]

(Where R ↑ 1, R ↑ 2, R ↑ 3, R ↑ 4
, M and n are as defined above, and R ↑ 5 represents a lower alkyl group. It is possible to obtain a lower aliphatic monocarboxylic acid ester of dienol represented by the formula (1).

The oxygen-containing olefin represented by the general formula (III), which is a starting material in the method of the present invention, is a known compound, and its representative compound, 2,2,5-trimethyl-4-hexene-1-a. Is, for example, by reacting prenyl halide and isobutyraldehyde in the presence of an alkali such as potassium hydroxide, or 2-methyl-
Add 3-butene-2-ol and isobutyraldehyde
It can be easily produced by reacting in the presence of an acidic catalyst such as toluenesulfonic acid or sulfuric acid [Oil Chemistry, Vol. 31, No. 5, pp. 295-299 (198).
2 years))].

In addition, the compounds of the general formula (IV-1) or (IV-
The organomagnesium compound represented by 2) is obtained by reacting the corresponding organic halide with metallic magnesium in an ether solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc. under an atmosphere of an inert gas such as nitrogen or helium. It can be manufactured.

The amount of magnesium metal used is about 1 to 5 times the atomic equivalent of the organic halide, preferably 1 to 1.
It is 5 times the atomic equivalent.

The reaction temperature is represented by the general formula (IV-1) or (I
When an organic halide corresponding to the organomagnesium compound in which n is 0 in V-2) is used as a raw material, it is -30 ° C to room temperature, preferably -20 ° C to + 20 ° C, and n is 1 When an organic halide corresponding to an organomagnesium compound is used as a raw material, the range of 0 ° C to the boiling point of the solvent used is preferable.

In order to smoothly carry out this reaction, it is preferable to activate the magnesium metal by adding iodine, alkyl bromide, alkylene dichloride and the like into the reaction system.

The reaction between the oxygen-containing olefin represented by the general formula (III) and the organomagnesium compound represented by the general formula (IV-1) or / and the organomagnesium compound represented by the general formula (IV-2) is usually carried out. , Tetrahydrofuran, diethyl ether, dimethoxyethane and the like. This reaction is conveniently carried out by dropping the oxygen-containing olefin into the preparation liquid of the organomagnesium compound obtained as described above.

The amount of the oxygen-containing olefin used is about 0.5 to 2 times the molar amount of the organic halide used to prepare the organomagnesium compound.

The reaction temperature is -40 ° C to + 50 ° C, preferably -20 ° C to + 20 ° C.

After completion of the reaction, the compound of the general formula (I
The separation and recovery of the dienols represented by -1) can be carried out by a general method. For example, the reaction mixture is poured into an aqueous solution of ammonium chloride, then diluted hydrochloric acid is added thereto, and then extracted with hexane or the like. The extract is washed with water, dried over magnesium sulfate, etc., the solvent is distilled off, and the residue is distilled under reduced pressure to obtain the desired dienol represented by the general formula (I-1). You can

The reaction between the diene represented by the general formula (I-1) and the lower aliphatic monocarboxylic acid or its reactive derivative can be carried out under general ester synthesis reaction conditions. Shows a typical example of the ester synthesis reaction.

(Reaction Example A) Reaction of Dienol with Lower Aliphatic Monocarboxylic Acid Diene and lower aliphatic monocarboxylic acid are mixed with benzene,
In an inert solvent such as toluene or xylene, for example, dicyclohexylcarbodiimide, or 2-chloro-1 iodide.
-Methylpyridinium is reacted with triethylamine, magnesium sulfate, molecular sieve or the like in the presence of a dehydrating condensing agent at room temperature or under heating, or by reacting under azeotropic dehydration conditions to obtain the desired dieno- It is possible to obtain a lower aliphatic monocarboxylic acid ester of vinyl alcohol.

(Reaction Example B) Reaction of Dienol with Lower Aliphatic Monocarboxylic Acid Halide Diene with lower aliphatic monocarboxylic acid halide, preferably chloride, with benzene, toluene, ether,
The desired dieno by reacting in the presence of a tertiary amine such as pyridine and triethylamine in an amount of 1 to 3 molar equivalents with respect to alcohol in an inert solvent such as chloroform at a temperature from room temperature to the boiling point of the solvent. It is possible to obtain a lower aliphatic monocarboxylic acid ester of

(Reaction Example C) Reaction of Dienol with Lower Aliphatic Monocarboxylic Acid Anhydride Diene and lower aliphatic monocarboxylic acid anhydride are placed in an inert solvent such as benzene, toluene, xylene or hexane. , Preferably in the presence of an acid such as sulfuric acid, p-toluenesulfonic acid or zinc chloride or a base such as pyridine, 4-dimethylaminopyridine, 4-pyrrolidinepyridine, triethylamine or sodium acetate, at room temperature or under heating. As a result, the desired lower aliphatic monocarboxylic acid ester of dienole can be obtained.

(Reaction Example D) Reaction of Dienol with Lower Alkyl Ester of Lower Aliphatic Monocarboxylic Acid Diene and lower alkyl ester of lower aliphatic monocarboxylic acid are combined with a suitable transesterification catalyst such as p- In the presence of a toluene compound such as toluene sulfonic acid or tetramethyl titanate, the reaction is carried out by heating in an inert solvent such as toluene or xylene, and the low boiling point alcohol generated is removed outside the reaction system. It is possible to obtain a lower aliphatic monocarboxylic acid ester of dienole.

(Reaction Example V) Reaction of Dienol with Enol Ester of Lower Carbonyl Compound Diene with an ester of lower carbonyl compound, for example isopropenyl acetate, is converted into a suitable transesterification catalyst such as p-toluene. In the presence of a sulfonic acid or a titanium compound such as tetramethyl titanate, the reaction is carried out by heating in an inert solvent such as toluene or xylene, and the resulting low-boiling lower carbonyl compound is removed to the outside of the reaction system. It is possible to obtain a lower aliphatic monocarboxylic acid ester of dienole.

Separation and recovery of the lower aliphatic monocarboxylic acid ester of dieanol obtained by the above ester synthesis reaction can be carried out by a usual method. For example, the reaction mixture is poured into water, then extracted with hexane and the like, the extract is washed with water, dried over magnesium sulfate and the like, after distilling off the solvent, the residue is distilled under reduced pressure,
It is possible to obtain the desired lower aliphatic monocarboxylic acid ester of dienole represented by the general formula (I-2).

As described above, the dienoles represented by the general formula (I) or the esters thereof have a very pleasant aroma and excellent adaptability to perfume. Therefore, for example, a perfume composition (perfume) is used.
It can also be used for aromatizing cosmetic products (soap, lotion, cream, etc.), aromatizing purifying agents or detergents, and the like.

The lower aliphatic monocarboxylic acid ester of dienole represented by the general formula (I-2) is, for example, the bicyclic alcohol represented by the general formula (II) or its lower aliphatic ester by the following method. Derived to monocarboxylic acid ester.

[0045]

[Chemical 14]

In the formula, A is the following formula

[0047]

[Chemical 15]

Represents a group represented by: R ↑ 1, R ↑ 2,
R ↑ 3, R ↑ 4, R ↑ 5, Y, m and n are as defined above, R represents a lower alkyl group, and M represents an alkali metal.

That is, a lower aliphatic monocarboxylic acid ester of a diene represented by the general formula (I-2) is used in a two-phase system of water and an organic solvent immiscible with water such as methylene chloride and chloroform. The chlorinated dieno-formula represented by the general formula (V) is obtained by reacting bleached powder and dry ice with hypochlorous acid generated in situ.
And then the chlorinated dienoyl ester relative to the alkali metal salt of a lower aliphatic monocarboxylic acid such as sodium acetate, potassium propionate or the like and the chlorinated dienoyl ester. About 1-5 mol% Pd [P (C ↓ 6H ↓ 5) ↓
3] In the presence of a zero-valent palladium complex such as ↓ 4, the lower aliphatic monocarboxylic acid to be produced is removed from the system and reacted by heating at about 150 to 250 ° C to hydrolyze the product as necessary. As a result, the bicyclic alcohol represented by the general formula (II) or a lower aliphatic monocarboxylic acid ester thereof can be obtained.

[0050]

EXAMPLES The present invention will be described below with reference to examples and reference examples.

Example 1 Synthesis of 3,3,5,5,8-pentamethyl-1,7-nonadiene-4-ol

[0052]

[Chemical 16]

Metallic magnesium 47.6 under nitrogen atmosphere
g (1.96 mol) of tetrahydrofuran 300 ml
In addition, 50 mg of iodine and 0.5 ml of 1,2-dibromoethane were added to this solution and stirred. When the color of iodine disappeared, the system was cooled to -5 ° C to -10 ° C, and a solution of 175 g (1.68 mol) of prenyl chloride in 500 ml of tetrahydrofuran was added dropwise to the above mixture with stirring. The dropping rate was adjusted so that the reaction temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 30 minutes, and then, while maintaining the internal temperature at 0 ° C., 147 g (1.05 mo) of 2,2,5-trimethyl-4-hexene-1-al was added to the reaction mixture.
A solution of 1) in 150 ml of tetrahydrofuran was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours, and then the reaction mixture was poured into a large amount of saturated ammonium chloride aqueous solution,
Dilute hydrochloric acid was added to the solid substance to dissolve it, and then diethyl ether was added.
It was extracted with tell. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was distilled under reduced pressure to obtain 3,3,5,5,8 having the following physical properties.
1-pentamethyl-1,7-nonadiene-4-ol
87 g (0.89 mol) was obtained. Yield 85% (2,2,
5-trimethyl-4-hexene-1-al basis). bp. : 63 ° C./0.1 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.90 (s, 6H); 1.09 (s, 6H);
1.17 (s, 1H); 1.57, 1.68 (each
bs, 6H); 1.8 to 2.3 (m, 2H); 3.1
6 (s, 1H); 4.8-5.1 (m, 2H); 5.1
6 (m, 1H); 5.97 (dd, J = 10 Hz and 1
8Hz, 1H) Mass spectrum m / e: 210 [M] ↑ +

Example 2 Synthesis of 3,3,5,5,8-pentamethyl-1,7-nonadiene-4-yl acetate

[0055]

[Chemical 17]

3,3,5,5,8-pentamethyl-1,
7-Nonadiene-4-ol 40.0 g (190 mmo
l), 50 ml (360 mmol) of triethylamine and 0.50 g of 4- (N, N-dimethylamino) pyridine.
In a mixed solution of (4.1 mmol), acetic anhydride 25 g (245
mmol) was slowly added dropwise. After stirring at room temperature for 16 hours, the reaction mixture was poured into water and extracted with diethyl ether. The extract was washed successively with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was distilled under reduced pressure to give the following physical properties 3,3.
5,5,8-Pentamethyl-1,7-nonadiene-4-
45.3 g (179 mmol) of yl acetate was obtained. Yield 94%. bp. : 87-94 ° C./0.5 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.81 (s, 6H); 0.96 (s, 3H);
1.01 (s, 3H); 1.47, 1.63 (each
bs, 6H); 1.75-2.0 (m, 2H);
95 (s, 3H); 4.63 (s, 1H); 4.7-
5.0 (m, 2H); 5.05 (m, 1H); 5.96
(Dd, J = 10 Hz and 18 Hz, 1 H) Mass spectrum m / e: 192 [M-CH ↓ 3 C
OOH] ↑ +

Example 3 3,5,5,8-Tetramethyl-1,7-nonadiene-
Synthesis of 4-ole

[0058]

[Chemical 18]

3.0 g of magnesium metal under nitrogen atmosphere
(123 mmol) was added to 20 ml of tetrahydrofuran, and 50 mg of iodine and 0.5 ml of 1,2-dibromoethane were added to this solution and stirred. When the color of iodine disappeared, the system was cooled to -5 ° C to -10 ° C, and a solution of 10.0 g (110 mmol) of crotyl chloride in 30 ml of tetrahydrofuran was added dropwise to the above mixture with stirring. The dropping rate was adjusted so that the reaction temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at 0 ° C for 30 minutes, and then 2,2,5-trimethyl-4-added to the reaction mixture while keeping the internal temperature at 0 ° C.
Hexen-1-al 10.8 g (78.0 mmol)
A solution of 10 ml of tetrahydrofuran was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours, poured into a large amount of saturated aqueous ammonium chloride solution, the solid was dissolved by adding dilute hydrochloric acid water, and then extracted with diethyl ether. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was distilled under reduced pressure to obtain 3,5,5,8-tetramethyl-1,7-nonadiene-4-ol having the following physical properties. 9.9 g (6
5.5 mmol) was obtained. Yield 84%. bp. : 95-100 ° C./3 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.82 (s, 6H); 1.03 (d, J = 7H
z, 3H); 1.37, 1.57 (each bs, 6
H); 1.68 (bs, 6H); 1.8 to 2.0 (m,
2H); 2.2-2.7 (m, 1H); 3.05-3.
2 (m, 1H); 4.8-5.3 (m, 3H); 5.6
~ 6.15 (m, 1H) Mass spectrum m / e: 196 [M] ↑ +

Example 4 3,5,5,8-Tetramethyl-1,7-nonadiene-
Synthesis of 4-yl acetate

[0061]

[Chemical 19]

3,5,5,8-Tetramethyl-1,7-
Nonadiene-4-ol 12.9 g (65.8 mmo)
1), 9.0 g (89 mmol) of triethylamine, 8.0 g (78 mmol) of acetic anhydride and 0.1 g (0.8 mmol) of 4- (N, N-dimethylamino) pyridine were dissolved in 20 ml of diethyl ether, and the mixture was allowed to stand at room temperature. I made it react overnight. By treating the reaction mixture in the same manner as in Example 2, 3,5,5,8- having the following physical properties was obtained.
Tetramethyl-1,7-nonadiene-4-ylacetate
(10.0 g (42 mmol)) was obtained. Yield 64%. bp. : 45-60 ° C./0.15 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.84 (s, 6H); 0.95 (d, J = 7H
z, 3H); 1.54, 1.69 (each bs, 6
H); 1.8 to 2.1 (m, 2H); 1.99 (s, 3)
H); 2.3 to 2.7 (m, 1H); 4.63 (m, 1)
H); 4.8-5.3 (m, 3H); 5.6-6.1.
(M, 1H) Mass spectrum m / e: 178 [M-CH ↓ 3 C
OOH] ↑ +

Example 5 Synthesis of 5,5,8-trimethyl-1,7-nonadiene-4-yl acetate

[0064]

[Chemical 20]

In Example 3, 10.0 g of crotyl chloride
8.4 g (1 mmol) of allyl chloride instead of (110 mmol)
(10 mmol) except that the reaction was performed in the same manner and the reaction mixture was treated in the same manner to obtain an ether extract. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate, and ether was distilled off therefrom to remove 5,5,8-trimethyl-1,7-nonadiene-4-. Crude product of ole 12.2
g (67.1 mmol) was obtained. This crude product was reacted in the same manner as in Example 4, and the reaction mixture was treated in the same manner to give 5,5,8-trimethyl-1,7-nonadien-4-ylacetate having the following physical properties. 1
5.0 g (66.9 mmol) was obtained. Yield 86%. bp. : 65 to 67 ° C./0.4 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.83 (s, 6H); 1.54, (each
bs, 6H); 1.8-1.95 (m, 2H); 1.9
2 (s, 3H); 2.0 to 2.4 (m, 2H); 4.6
5 to 5.25 (m, 4H); 5.45 to 5.9 (m, 1)
H) Mass spectrum m / e: 164 [M-CH ↓ 3 C
OOH] ↑ +

Example 6 3-Isopropyl-5,5,8-trimethyl-1,7-
Synthesis of nonadiene-4-ylacetate

[0067]

[Chemical 21]

In Example 3, 10.0 g of crotyl chloride
The ether extract was obtained by reacting in the same manner except that 17.9 g (110 mmol) of 1-bromo-4-methyl-2-pentene was used instead of (110 mmol), and treating the reaction mixture in the same manner. Obtained. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate, and ether was distilled off from this to give 3-isopropyl-5,5,8-trimethyl-.
11.4 g of crude product of 1,7-nonadiene-4-ol
(50.8 mmol) was obtained. This crude product was used in Example 4.
3-isopropyl- having the following physical properties by reacting in the same manner as above and treating the reaction mixture in the same manner.
13.1 g (49.2 mmol) of 5,5,8-trimethyl-1,7-nonadiene-4-yl acetate was obtained. Yield 63%. bp. : 77 to 83 ° C./0.25 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.75, 0.88 (each d, J = 6.5)
Hz, 6H); 0.81 (s, 6H); 1.54, 1.
67 (each bs, 6H); 1.25-1.7.
(M, 1H); 1.8 to 2.2 (m, 3H); 1.98
(S, 3H); 4.8 to 5.25 (m, 4H); 5.5
〜5.95 (m, 1H) Mass spectrum m / e: 206 [M-CH ↓ 3 C
OOH] ↑ +

Example 7 3,3,5,9-Tetramethyl-1,8-decadiene-
Synthesis of 4-ole

[0070]

[Chemical formula 22]

In Example 1, 147 g (1.05 mo) of 2,2,5-trimethyl-4-hexene-1-al
The following physical properties were obtained by reacting in the same manner except that 147 g (1.05 mol) of 2,6-dimethyl-5-heptene-1-al was used instead of l), and treating the reaction mixture in the same manner. 6,3 g of 3,3,5,9-tetramethyl-1,8-decadiene-4-ol having
05 mmol) was obtained. Yield 29%. bp. : 60 to 65 ° C./0.5 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.75 (d, J = 7 Hz, 3H); 0.97
(S, 6H); 0.9 to 1.5 (m, 4H); 1.5
4, 1.62 (each bs, 6H); 1.7-2.
05 (m, 2H); 3.0-3.15 (m, 1H);
4.75-5.2 (m, 3H); 5.85 (dd, J =
10 Hz and 18 Hz, 1H) Mass spectrum m / e: 210 [M] ↑ +

Example 8 3,3,5,9-tetramethyl-1,8-decadiene-
Synthesis of 4-yl acetate

[0073]

[Chemical formula 23]

In Example 2, 3,3,5,5,8-pentamethyl-1,7-nonadiene-4-ol 40.0
40.0 g of 3,3,5,9-tetramethyl-1,8-decadiene-4-ol instead of g (190 mmol)
By reacting in the same manner except using (190 mmol) and treating the reaction mixture in the same manner, 3,3,5,9-tetramethyl-1,8 having the following physical properties is obtained.
-Decadiene-4-yl acetate 32.6 g (12
9 mmol) was obtained. Yield 68%. bp. : 83 to 84 ° C./0.35 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.77 (d, J = 7 Hz, 3H); 0.96
(S, 6H); 1.0 to 1.4 (m, 3H); 1.5
4, 1.62 (each bs, 6H); 1.7-2.
05 (m, 2H); 1.97 (s, 3H); 4.5-
4.7 (m, 1H); 4.8-5.1 (m, 3H);
5.86 (dd, J = 10 Hz and 18 Hz, 1 H) Mass spectrum m / e: 192 [M-CH ↓ 3 C
OOH] ↑ +

Example 9 Synthesis of 3,3,9-trimethyl-1,8-decadiene-5-ol

[0076]

[Chemical formula 24]

In Example 1, 147 g (1.05 mo) of 2,2,5-trimethyl-4-hexene-1-al
By reacting in the same manner except that 133 g (1.05 mol) of 6-methyl-1,2-epoxy-5-heptene is used instead of 1) and treating the reaction mixture in the same manner, the following physical properties are obtained. 3,3,9-trimethyl-
179 g (0.91) of 1,8-decadiene-5-ol
2 mol) was obtained. Yield 87%. bp. : 96 to 102 ° C./3 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 1.00 (s, 6H); 1.2 to 1.8 (m, 4)
H); 1.54, 1.61 (each bs, 6H);
1.8-2.1 (m, 3H); 3.45-3.8 (m,
1H); 4.8-5.2 (m, 3H); 5.86 (d
d, J = 10 Hz and 18 Hz, 1H) Mass spectrum m / e: 196 [M] ↑ +

Example 10 Synthesis of 3,3,9-trimethyl-1,8-decadien-5-yl acetate

[0079]

[Chemical 25]

In Example 2, 3,3,5,5,8-pentamethyl-1,7-nonadiene-4-ol 40.0
Instead of g (190 mmol), 3,3,9-trimethyl-1,8-decadiene-5-ol 37.3 g (190
(3 mmol)) and reacted in the same manner and treating the reaction mixture in the same manner to give 3,3,9-trimethyl-1,8-decadiene-5 having the following physical properties.
30.3 g (127 mmol) of -yl acetate was obtained. Yield 67%. bp. : 109 to 112 ° C./4 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.96 (s, 6H); 1.25 to 1.65
(M, 4H); 1.52, 1.60 (each bs,
6H); 1.7-2.0 (m, 2H); 1.90 (s,
3H); 4.7 to 5.1 (m, 4H); 5.70 (d
d, J = 10 Hz and 18 Hz, 1 H) Mass spectrum m / e: 178 [M-CH ↓ 3 C
OOH] ↑ +

Example 11 Synthesis of 6,6,9-trimethyl-1,8-decadien-5-yl acetate

[0082]

[Chemical formula 26]

3.0 g of magnesium metal under a nitrogen atmosphere
(123 mmol) was added to 20 ml of tetrahydrofuran, and 50 mg of iodine and 0.5 ml of 1,2-dibromoethane were added to this solution and stirred. When the iodine color disappeared, 1-bromo-3-butene 14.9 was added to the above mixture.
A part of a solution of g (110 mmol) in 30 ml of tetrahydrofuran was added dropwise with stirring at room temperature to start the reaction, and then the remaining tetrahydrofuran solution of 1-bromo-3-butene was slowly refluxed in the reaction solution. Dropped at a rate. After completion of dropping, the system was heated to reflux for 1 hour, and then the system was cooled
The reaction mixture was cooled to 0 ° C. and 10.8 g (78.0 mm) of 2,2,5-trimethyl-4-hexene-1-al was added to the reaction mixture.
ol) in 10 ml of tetrahydrofuran was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours, and then the reaction mixture was poured into a large amount of saturated ammonium chloride aqueous solution,
Dilute hydrochloric acid was added to the solid substance to dissolve it, and then diethyl ether was added.
It was extracted with tell. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The ether was distilled off under reduced pressure to obtain a crude product of 6,6,9-trimethyl-1,8-decadiene-5-ol. By reacting this crude product with acetic anhydride in the same manner as in Example 4, 6,6,9 having the following physical properties was obtained.
8.0 g (33.6 mmol) of -trimethyl-1,8-decadien-5-yl acetate was obtained. Yield 43
%. bp. : 74 to 77 ° C./0.35 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.80 (s, 6H); 1.4 to 1.7 (m, 2)
H); 1.54, 1.67 (each bs, 6H);
1.7-2.1 (m, 4H); 1.96 (s, 3H);
4.6-5.25 (m, 4H); 5.5-6.0 (m,
1H) Mass spectrum m / e: 178 [M-CH ↓ 3 C
OOH] ↑ +

Reference Example 1 Fouger-based fragrance composition A fragrance composition having a Fuzea-like aroma was obtained by the following formulation.

[0085]

[Table 1]

Reference Example 2 Chypre-based fragrance composition A fragrance composition having a Fancy-like sypre-like aroma was obtained by the following formulation.

[0087]

[Table 2]

Reference Example 3 7-chloro-3,3,5,5,8-pentamethyl-1,
Synthesis of 8-nonadien-4-yl acetate

[0089]

[Chemical 27]

25.0 g of bleaching powder (60% available chlorine) was added to 100 ml of distilled water, and the mixture was stirred for a while, then, this solution was mixed with 3,3,5,5,8-pentamethyl-
1,7-Nonadien-4-yl acetate 44.2 g
(175 mmol) and 400 ml of methylene chloride were added. This mixed solution was ice-cooled, and a small piece of dry ice was gradually added to the mixed solution while stirring so that the internal temperature was kept at 3 to 8 ° C. When no more exotherm was observed, addition of dry ice was stopped, the mixture was stirred at the same temperature for a while, and then the reaction mixture was separated. The aqueous layer was extracted with methylene chloride, the extract and the organic layer were combined, washed successively with aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. Then, methylene chloride was distilled off from this organic layer, and the residue was distilled under reduced pressure to give 7-chloro-3,3,5,5,8-pentamethyl-1,8-nonadiene-4 having the following physical properties. -Il acetate 36.7g (128m
mol) was obtained. Yield 73%. bp. : 110 to 120 ° C./0.4 mmHg NMR spectrum (90 MHz, CCl ↓ 4, HMS)
δ: 0.85 to 1.05 (m, 12H); 1.73
(Bs, 3H); 1.82 (d, J = 6Hz, 2H);
1.96, 1.99 (s, diastereomeric
c, 3H); 4.45 (t, J = 6Hz, 1H);
60, 4.66 (s, diastereomeric,
1H); 4.55-5.05 (m, 4H); 5.95,
5.98 (dd, diastereomeric, J =
10 Hz and 18 Hz, 1H) Mass spectrum m / e: 226 [M-CH ↓ 3
COOH] ↑ +

Reference Example 4 1,1,3,3,6-pentamethyl-2,3,3a,
Synthesis of 4,5,7a-hexahydro-1H-inden-2-yl acetate

[0092]

[Chemical 28]

In a 100 ml volumetric flask equipped with a distiller, 287 mg (1.28 mmol) of palladium acetate and 2.70 g (10.3 mmo) of triphenylphosphine.
l), 12.6 g (154 mmol) of sodium acetate,
7-chloro-3,3,5,5,8-pentamethyl-1,
8-Nonadien-4-yl acetate 36.7 g (1
23 mmol) and 5 ml of benzene were added, the mixture was stirred under reduced pressure (110 Torr) while gradually raising the temperature to distill off benzene, and then reacted at 170 ° C. for 20 minutes while distilling out acetic acid. After cooling, the reaction mixture was poured into water and extracted with diethyl ether. The extract was washed successively with aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. Then, extract from this extract
The tel was distilled off, and the residue was distilled under reduced pressure to give 1,1,3,3,6-pentamethyl- having the following physical properties.
26.3 g (105 m) of 2,3,3a, 4,5,7a-hexahydro-1H-inden-2-yl acetate
mol) was obtained. Yield 82%. bp. : 90-92 ° C / 0.45mmHg NMR spectrum (90MHz, CCl ↓ 4, HMS)
δ: 0.7 to 1.15 (m, 12H); 1.2 to 2.
0 (m, 6H); 1.60 (bs, 3H); 2.00
(S, 3H); 4.45, 4.59 (s, diaste
5.30 (bs, 1H) Mass spectrum m / e: 190 [M-CH ↓ 3
COOH] ↑ +

Reference Example 5 Woody Base A base having a woody aroma according to the following formulation.
I got a su.

[0095]

[Table 3]

Reference Example 6 Modern Fragrance Composition A fragrance composition having a modern style fragrance was obtained by the following formulation.

[0097]

[Table 4]

[0098]

Industrial Applicability The present invention provides a novel dienole or its ester, which is useful as an aroma component of various perfume compositions, and a process for producing them. The dienole or its ester provided by the present invention is also useful as a synthetic intermediate for a bicyclic alcohol or its lower aliphatic monocarboxylic acid ester, which is useful as an aroma component of various perfume compositions. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C11B 9/00 S 2115-4H // C07C 29/36

Claims (2)

[Claims] 1. A general formula: (In the formula, R ↑ 1, R ↑ 2, R ↑ 3 and R ↑ 4 are the same or different and each represents a hydrogen atom or a lower alkyl group; Y
Represents a hydrogen atom or a lower acyl group; m represents an integer of 1 or 2; n represents an integer of 0 or 1. ) Dienol or ester thereof. 2. A general formula: (In the formula, R ↑ 1 and R ↑ 2 are the same or different and each represents a hydrogen atom or a lower alkyl group; l represents an integer of 0 or 1; m represents an integer of 1 or 2). The oxygen-containing olefin is represented by the general formula: (In the formula, R ↑ 3 and R ↑ 4 are the same or different and each represents a hydrogen atom or a lower alkyl group; X represents a halogen atom; and n represents an integer of 0 or 1). Or / and the general formula: (In the formula, R ↑ 3, R ↑ 4, X and n are as defined above.) By reacting with an organomagnesium compound represented by the general formula: (In the formula, R ↑ 1, R ↑ 2, R ↑ 3, R ↑ 4, m and n are as defined above.), And if necessary, the diene is lower. A general formula characterized by reacting with an aliphatic monocarboxylic acid or a reactive derivative thereof (Wherein R ↑ 1, R ↑ 2, R ↑ 3, R ↑ 4, m and n are as defined above, and Y represents a hydrogen atom or a lower acyl group.) Or A method for producing the ester.